Yarn conditioning process and composition therefor



Patented Apr. 14, 1942 YARN CONDITIONING PROCESS AND COMPOSITION THEREFOR Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application October 9, 1940, Serial No. 360,454

18 Claims.

This invention relates to the treatment of cellulose organic derivative filaments, fibers, threads and the like and more particularly to a method of eliminating the tendency of such materials to accumulate charges of static electricity in twisting, winding and spinning. The invention also relates particularly to the treatment of cellulose organic derivative cut staple fibers to adapt them for the manufacture of spun yarns.

As is well known, cellulose organic derivative materials, particularly in filament, yarn, or sheet form, are particularly subject to the accumulation on their surfaces of charges of static electricity from frictional and other influences. In the case of filaments and yarns in which the surface area of the material (per unit of weight) is enormously greater as compared to sheets or films, the problem of static often assumes serious proportions. In the manufacture of yarns of various types from artificial filaments, numerous steps in which the yarn is subjected to frictional influences may be necessary, as for example, twisting, winding, warping, carding, combing, drawing, spinning and the like, all of which operations tend to produce large accumulations of static on the filaments. This is particularly aggravated in the utilization of cut staple, as for example, in the making of spun yarn, since in carding and combing considerable friction is developcd and as a result sufiicient charges accumulale on the fibers to make the formation of the web difficult, if not impossible; furthermore, even if a web is formed with some degree of success, the subsequent drafting operation produccs a very uneven spun yarn or intermediate roving due to the presence of the static charge. In addition, there is the ever-present fire hazard. Cellulose derivative yarn, particularly in the form of cut staple, is extremely difiicult to handle in the various operations involved in making spun yarn, not only because such material is composed of filaments having smooth, glass-like surfaces without natural kink or irregularity, but also because it has relatively negligible moisture content at normal humidities, as compared to natural fibers such as cotton and wool, making it inherently far more susceptible to the accumulation of static. The charges accumulating on cellulose derivative cut staple fibers are, under some circumstances, even sufiicient to separate the individual fibers a distance of inches, notwithstanding their relatively minute size.

This invention has as its principal object to provide an improved method for the treatment of cellulose organic derivative yarns to reduce or eliminate the tendency of such yarns to accumulate charges of electricity under frictional and other influences. A further object is to provide a method of facilitating the handling and employment of cellulose organic derivative cut staple fibers in the various operations involved in the manufacture of spun yarns. A still further object is to provide a method of treating cellulose organic derivative yarns in either filament or cut staple form, wherein the material is simultaneously softened and lubricated and the accumulation of static charges thereon is prevented. Another object is to provide an improved type of cellulose organic derivative cut staple having little or no tendency toward accumulation of static electrical charges. Other objects will appear hereinafter.

These objects are accomplished by the following invention whlch in its broader aspects comprises applying to cellulose organic derivative yarns either in the form of filaments, threads or staple fibers, an anti-static composition characterized by the presence therein of salts of dialkyl phosphonic acids, said acids having the general formula:

wherein R and R are substituents selected from the group consisting of hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyl, cycloalkyl, aryl and heterocyclic groups and hydrogen, and Z is hydrogen or a salt-forming radical, and wherein R, R, R and R may be part of a cyclic system of carbon atoms. The alkyl group may be selected from methyl, ethyl, butyl, cycloalkyl, benzyl, cetyl, ethoxyethyl, allyl and tetrahydrofurfuryl and the like. The aryl group may be phenyl, zenyl, naphthyl and furyl, etc.

These compounds may be prepared as described in Compt. rend., 134,847; Ann. Chim. Phys. 8, 3,347; Compt. rend., 133,219.

In accordance with our invention the above mentioned salts of dialkyl phosphonic acids may be applied to the yarn in any convenient mannet, for example, by roll, wick, immersion, spraying or the like. Inasmuch as these compounds are soluble in oil they may be dissolved or dispersed in oils such as mineral oil, blown and unblown, drying and semi-drying, vegetable and animal oils, examples of which are light mineral, neatss-foot, olive, teaseed, castor, soya bean, rapeseed oils, and other lubricants.

In the following examples and description, we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

Example 1 Example; Cm 99-100 parts blown olive oil c-1 -c diethanolaminesult 140 parts 5 OCO-CH: 0111 0H 0 CH: 7 CHPOH,

OH on (Bis-bcta'hydroxy propane-beta-lp';iosplionic acid dicthanolamine set A conditioning liquid is made up as follows:

Butyl naphthenate, 90-95 parts 10 5 parts Cans 0 OH C2 5 (Bis-beta-hydroxy butanc-beta-phosphonic acid dictbylcyclohcxyl. 3U

amine salt) and applied to textile materials such as silk, wool, cellulose acetate, etc., as described in Example 1. If the yarn is intended primarily for knitting, the amount of conditioning liquid applied may vary from 4-25% by weight of the yarn, and if for weaving between 1-5 by weight of the yarn.

Cellulose acetate filaments treated as described above are quite soft and pliable and give improved results in various textile operations such as weaving, knitting, etc., and especially in the production of cut staple fibers.

Conditioning liquids particularly useful for the treatment of various types of yarns in accordance with our invention particularly those composed of or containing cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate,

and similar organic acid esters, and especially adapted for the deelectrification 0r anti-static treatment of cellulose organic derivative cut staple yarns are as follows:

Example 3 1-10 parts CH3\(|)H OH/Clia /C; I)\ C411 0 ONHA Cant (Bls-betu-hydroxy pentane-betlagphosphonlc acid ammonium 99-90 parts mineral oil Example 4 10 parts butyl naphthenate 89-80 parts mineral oil 1-10 parts 0 C ll ll C P-C di-bela-mcthoxyetliylammv l salt cb ll 5 11 H OH H (Alphaphenyl alpha'hydroxy-pentanc alplia-cyr-iohm yl-ulpl m l lydroxy hciouc-alplia-pliosplionic acid (ii-butamuihoay clllfl-nluim' 53 t) CII2CH: 1

Cyclnhexylamine-l-l01? (Bis-aliilia-acctoxycyclohexyl-alphn-phusphonic acid cyclohcxylamine salt) Example 6 -99 parts olive oil 20-1 parts diamylamine salt (Alplie-mothyl-alpha-propoxydecane-elpha-hydroxyfurluryl-alplia, alpha-phosphonic acid diamylamine salt) Example 7 90-99 parts neats-foot oil 10-1 parts 011 on l/CHPCH: L'I JI /PC (Alplia-mcthylalpha-hydroxy hexadecyl-alpha-hydroxy-cyclohcxyl pliosphunic acid tetrahydrofuriurylamine salt) (Alpha-methyl-alpba-oleyloxyhcptanc-alpha-hydroxy-alphanaphthenyl methyl phosphonic acid morpholeiie salt) Butyl stearate, 20 parts Mineral oil, 20 parts Example 10 Blown sperm oil, 77-68 parts l-l0 parts H2O CHz-CH: Cilia (Beta-liydroxy-beta-tetrahydrot'nrfuryl p0ntyl-nlpha-hydroxy-bciaphenyl eihanc phospliuuic acid potassium salt Water, 2 parts Di-beta-methoxyethylsuccinate, .20 parts Example 11 Teaseed oil, 99-90 parts 1-10 parts H CH:O-CHz-(BCH1 0=P0H our-om CHCH\ /CH:

11 our-4m,

(Bcta-hydroxy-alpha-rnethoxy propyl-omega-hydroxy-hexahydrobenzyl pliosphonlc acid) Example 12 (Al iha-hydroxy-alpha-acctoxy cyclobuiyl-phosphmiic acid iricthauulaxnule salt) Example 13 1-10 parts OH C-- PC S0111 1 il Cll; on 0 Ha O ll'tctramcthylammonium hydroxide (llctn-hydroxy 1iropyH)cta-hydroxy-beta-phcnyl (p sull'onic acidl phosphouic acid tetramcthylammomum hydroxide suit) Blown olive oil, parts Blown neats-foot oil, 69-60 parts Example 14 Olive oil, 50 parts Sulfonated castor oil, 10 parts Mineral oil, 20 parts Oleic acid, 1045 parts 5 parts Clix CgHs

O H-diluriurylarninc (l5lsbctn-hydroxybuianc phosphonic acid difurlurylamine salt) Example 15 '70 parts water 15 parts water soluble cellulose ester 10 parts sulfonated olive oil 5 parts C ll 2 5 OH.trii-thylamine ((lmiinm-li \'drm v puntmic-alpha-hydroxy methane phosphonic acid Lrioihylamine salt) Example 16 One pound l-methylamino 4 ethylamino-anthraquinone is ground with M; pound 0511., l 0 out cm {llis-fi-hylroxy uiuli-cyl pliosplionic acid Sullilllll salt) and 3 pounds of sugar; The resulting finely divided mixture is then added to 100 gallons of water heated to -90. The resulting aqueous suspension of blue -dye is then used to dye about pounds of cellulose acetate deep blue shades. 7

Example 17 One pound of o-ethoxybenzene azo barbituric acid is ground'with pound of OlI-triethanolmninc salt lliis-hchrliydroxy propane phosphonic acid triviluinolamine salt) and 3 pounds of sugar as in Example 16. The resulting finely divided mixture is poured into water (100 gallons) heated to 80-85 and used to dye 100 pounds of cellulose acetate greenish-yellow shades in any desired manner.

As will be evident from a consideration of Examples 16 and 17, the conditioning agents of our invention may be used efiectively as dispersing agents for dyes. These agents also have exceptional value in other relationships in which emulsifyng and dispersing power are important. In other words, they may be employed for a wide variety of uses in the textile industry.

Any of the above compositions may be applied to the yarn intended for use in circular knitting by means of a bath, wick, spray, roller, pad or any suitable means. The amount of conditicning liquid applied may vary between 5-25% by weight of the yarn. Usually, however, the amount of conditioning liquid applied is about 10-15% by weight of the yarn. Yarn composed of cellulose acetate conditioned as described above gives excellentresults when used in the circular knitting process.

If the conditioning agent is to be applied to the yarn after spinning, this may be done by bringing the yarn in contact with a wick, roll, or felt wet therewith, or the liquid may be applied' by immersion, spray, or otherwise. The particular point at which the liquid is applied may vary. It may. for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the godet or other roll or guide and the point of winding and/or twisting. -In some cases, the liquid may even be applied to the yarn after winding onto cones, spools, bobbins, or the like or by the so-called bobbin to bobbin" method.

In the case of staple fiber manufacture, the liq= uid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent 0 employed will vary widely depending upon the results desired, the specific nature of the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where a cellulose organic acid ester yarn such as a yarn composed of cellulose acetate, is intended for knitting, about 4 to 25% or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about 1 and 5%.

Although in the above examples we have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such as solvents, non-solvents, emulsifying agents, blending agents and the like, may be added within the scope of our invention. Likewise, various dyes or other coloring matter may be included in case it is desired to permanently or fugitively tint or dye the material undergoing treatment.

Although we have found it convenient to illustrate our invention by reference to compositions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it is desired to control the deelectrifying action of the conditioning agent, the amount of the agent may be adjusted as, for example, by reducing the amount of the agent and correspondingly increasing the amount of oil or other ingredient.

While we have described our invention with particular reference to the treatment of yarns composed of organic derivatives of cellulose such as cellulose acetate, the conditioning agents and formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as those composed of or containing cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

The term yarn as used herein and in the claims is to be understood as including a single filament. a plurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture of natural and artificial filaments or a composite thread formed by twisting together individual strands of natural or artificial materials,'as well as cut staple fiber produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditioning agents of our invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor, neats-foot, sperm and other oils. This enables them to be used with any of such oils in making up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and compositions of our invention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to deelectrify yarns, especially those composed of or containing organic derivatives of cellulose such as cellulose acetate and render them amenable to various textile operations, especially operations such as those involved in the manufacture of cut staple fibers, as well as the manufacture of yarns adapted for weaving and knitting. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns. In addition, due to their solubliity in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. 7

Of the above compositions we have found that bis-beta-hydroxy propane-beta-phosphonic acid diethanolamine salt, bis-beta-hydroxy butanebeta-phosphonic acid diethylcycloh-exylamine salt, and bls-beta-hydroXy pentane-beta-phosphonic acid ammonium salt are outstanding in wherein R and R. are substituents selected from the group consisting of hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyl, cycloalkyl, and heterocyclic groups and hydrogen, and Z is a substituent selccted from the group consisting of hydrogen and salt-forming radicals.

2. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential anti-static component a salt of a dialkyl phosphonic acid having the general formula:

wherein R and R are substituents selected from the group consisting of hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyl, cycloalkyl, and heterocyclic groups and hydrogen, and Z is a substituent selected from the group consisting of hydrogen and salt-forming radicals.

3. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing cellulose acetate to accumulate charges of static electricity, which comprises applying there-' to a composition containing as its essential antistatic component a salt of a dialkyl phosphonic acid having the general formula:

wherein R and R are substituents selected from the group consisting of hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyl, cycloalkyl, and heterocyclic groups and hydrogen, and Z is a substituent selected from the group consisting of hydrogen and salt-forming radicals.

4. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential anti-static component bis-beta-hydroxy propane-beta-phosphonic acid diethanolamine salt.

5. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate nium salt.

aerasoz charges oistatic electricity; which comprises lapplying thereto a composition.containing:asrits essential anti-static component bis-beta-hydxoxy: butane-beta-phosphonic acid diethylcyclohexyla-l minesalt. Y ur-1 6. The method of eliminating the tendency of yarns, filaments or fibers composed of or containing organic derivatives of cellulose to accumulate charges of static electricity, which comprises applying thereto a composition containing as its essential antistatic component bis-betahydroxy pentane-beta-phosphonic acid aming);

'7. An anti-staticcomposition adapted. when applied to textile yarns, filaments or fihers to eliminate the tendency of such materials to accomponent a salt of a dialkylphosphonicf acid having the general formula:

W a i ll-C----P-C-R oz 0 on wherein R and R are substituents selected from the group consisting of hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyl, cycloalkyl, and heterocyclic groups and hydrogen, and Z is a substituent selected from the group consisting of hydrogen and Salt-forming radicals.

9. An anti-static composition adapted. when applied to cellulose acetate yarns, filaments or fibers. to eliminate the tendency of such materials to accumulate charges of static electricity, said composition containing as its essential antistatic component a salt of a dialkyl phosphonic acid having the general formula:

wherein R and R are substituents selected from cu the group consisting of hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyLcycloalkyLand hcterocyclic groups and hydrogen. and Zis a substituent selected from the group consisting of hydrogen and salt-forming radicals.

10. An anti-static composition adapted, when applied to cellulose organic derivative yarns, filaments, or fibers, to eliminate the tendency of such materials to accumulate charges of static cumulate charges of static electricity, said corn-, position containing as its essential anti-static electricity; sa'iddompbsitionvcontaining; as its essential antt-statidco'mpdneritt bisabeta hydroxypropane-beta-phosphonic acid diethanolamine saltr- 1 our.

- 11;. An anti-staticcomposition adapted, when applied to cellulose organic tlerivative yarns, filaments or fibeisflt'o eliminate-the tende'ncy of such materials "to accumulate charges 5 of static electricity, said composition containing as its essen- 10 tial anti-static component bis-beta-hydroxy butane-beta-phosphonic acid-diethyl-cyclohexylm naret-Hi, 121 A 'anti-static composition adapted, when applied to cellulose organic derivati-vdyarm, filainentsor fillers, to eliminate the tendency of such "materials tdacciimulate charges of static electricity. said composition containing as its essential ant static component.bis-beta-hydroxy pen- [tane-ce a-pho sphonicsacid ammonium salt.

13. Textile yarns having a lessened tendency to accumulatech arges of static electricity, said yarns containinga-salt of a dialkyi phosphonic acid having the general formula:

It It I 0 l l H wherein R and R are substituents selected from the group consisting of hydrogen and alkyl and I R and R are substituents selected from the group consisting of alkyl, cycloalkyl, and hcterocyclic groups and hydrogen. and Z is a substituent selected from the group consisting of hydrogen and salt-forming radicals.

15. Textile yarns composed of or containing cellulose acetate having a lessened tendency to accumulate charges of static electricity, said yarns containing a salt of a dialkyl phosphonic acid having the general formula:

wherein R and R'-' arc substituents selected from the group consisting oi hydrogen and alkyl and R and R are substituents selected from the group consisting of alkyl, cycioalkyl, and heterocyclic groups and hydrogen. and Z is a substituent se lected from the group consisting of hydrogen and salt-forming radicals.

16. Textile yarns composed of or containing organic derivatives of cellulose having a lessened 7,1 tendency to accumulate charges of static electricky, said yarns containing bis-beta hydroxy propane-beta phosphonic acid diethanolamine sE-1t;-

17. Textile yarns composed of or containing organic derivatives of cellulose-having a lessened tendency to accumulatechargesof static electricity, said yarns containing bis-beta-hydroxy butane-beta-phosphonic aciddiethylcyclohexylaminesalt- Hm I tricity, said yarns containing bis-be'ta-hydzoxy 5 pentane-beta-phosphonlc acid ammonium salt-Z JOSEPH B; memen- JAMES G. MCNALLYI;

l Certificate of Correction X April 14, 1942}: JOSEPH .B. DICKEY ET AL. It is hereby'eertified that'errors appear in the printed specification of 'the above numbered patent requiring correction as follows: Page 2, second column, line 2, for

l and that the said Lelzters Patenl; should be read with corrections therein Jthallf, h

99-100 parts read 99-90 parts} lines 66 to 71 inclusive, for

H1CCHI I H: H:CHrC4Ho H o 0 \PCCHO \6 o H read mc--cm H; H-om-c-cm. I Y a the same may conform to the record of the case in the Patent Oflice, Signed and sealed this 11th day of August, A. D. 1942.

[sEhL] HENRY VAN ABSDALE,

Acting Commissioner of Patents. 

